Thiophenol → Benzo(b)thiophene-2,3-dione

HRID 369609Notes

Reaction equation

HRID 369609 reaction equation
[C:1]1([SH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[C:8](Cl)(=[O:12])[C:9](Cl)=[O:10].[Cl-].[Al+3].[Cl-].[Cl-]>CCOCC>[S:7]1[C:1]2[CH:6]=[CH:5][CH:4]=[CH:3][C:2]=2[C:9](=[O:10])[C:8]1=[O:12]

Participants

5

Reactant 3

HCID 7969ThiophenolHCID 65578Oxalyl chlorideHCID 6451240Aluminum(III) Chloride

Product 1

HCID 97303Benzo(b)thiophene-2,3-dioneYield 69%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
0 °C

Procedure

To a solution of thiophenol (100 g, 0.907 mol) in ether is added dropwise a solution of oxalyl chloride (175 g, 1.38 mol) in ether. The mixture is stirred two hours at reflux and concentrated in vacuo. The residue is taken up in methylene chloride and cooled to 0° C. Aluminum chloride (145 g, 1.09 mol) is added in portions such that the temperature does not exceed 25° C. The resultant mixture is stirred 30 minutes at reflux, cooled to room temperature and poured into ice water with stirring. The organic layer is washed with saturated sodium bicarbonate, water and brine, dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo to an orange solid which is recrystallized from methylene chloride:hexanes to afford the title compound (102 g, 69.0%) which is identified by NMR spectral analysis.

Workup

  1. temperatureat reflux
  2. concentrationconcentrated in vacuo
  3. customdoes not exceed 25° C
  4. temperatureat reflux
  5. temperaturecooled to room temperature
  6. stirringwith stirring
  7. washThe organic layer is washed with saturated sodium bicarbonate, water and brine
  8. dry with materialdried over anhydrous magnesium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo to an orange solid which
  11. customis recrystallized from methylene chloride

Sources & evidence

ORD record
ord-987969cad57d4e5c85a7cfe6b422bce2
Source dataset
uspto-grants-2000_10
Patent number
US06140270

Reaction notes

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